The invention relates to new pyridinylpyrimidine derivatives, to a plurality of processes for their preparation, and to their use as pesticides, in particular as fungicides.
It is known that certain pyridinylpyrimidine derivatives, such as, for example, 2-(6-methyl-2-pyridinyl)-4-o-tolylpyrimidine, 2-(6-methyl-2-pyridinyl)-4-hydroxy-6-phenylpyrimidine (cf. EP 0,270,362)and 2-(6-phenyl-2-pyridinyl)-4-chloro-6-methylpyrimidine (cf. EP 0,259,139), have fungicidal properties.
However, the fungicidal activity of these previously known compounds is not entirely satisfactory in all fields of application.
4-Phenyl-2-(2-pyridyl)-pyrimidine and 4-chloro-6-phenyl-2-(2-pyridyl)-pyrimidine (cf. J. Org. Chem. 32 (5), 1591-6 (1967)) are furthermore known. However, nothing is reported about the physiological activity of these compounds.
New pyridinylpyrimidine derivatives of the general formula (I) ##STR3## in which R.sup.1 represents hydrogen, halogen, alkoxy, alkylthio, halogenoalkyl, amino or dialkylamino, where, in the case of dialkylamino, the two radicals may, together with the nitrogen to which they are bonded, form a 5- to 7-membered, saturated or unsaturated ring which optionally contains a further hetero atom and which is optionally substituted by 1 or 2 alkyl groups;
in which furthermore
R.sup.1 represents in each case optionally substituted aryloxy, arylthio, aralkyloxy or aralkylthio, PA1 R.sup.2 and R.sup.3 are independent of one another and are identical or different and in each case represent hydrogen, halogen, alkyl, halogenoalkyl, alkoxy, alkylthio or alkoxycarbonyl, PA1 R.sup.2 and R.sup.3 together represent an alkylene chain having 3 to 6 carbon atoms which are linked via the ring positions 3 and 4 or 4 and 5, PA1 R.sup.4 represents hydrogen, halogen, alkyl, halogenoalkyl, hydroxyl, alkoxy, mercapto, alkylthio, amino or (di)-alkylamino, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- to 7-membered, saturated or unsaturated ring which optionally contains a further hetero atom and which is optionally substituted by 1 or 2 alkyl groups; or PA1 R.sup.4 represents alkenyloxy or alkynyloxy, PA1 R.sup.5 represents hydrogen or alkyl and PA1 Ar represents unsubstituted or substituted aryl, have been found, with the exception of the compounds 4-phenyl-2-(2-pyridyl)-pyrimidine and 4-chloro-6-phenyl-2-(2-pyridyl)-pyrimidine (disclosed in J. Org. Chem. 32 (5), 1591-6 (1967)). PA1 R.sup.1 represents in each case optionally substituted aryloxy, arylthio, aralkyloxy or aralkylthio, PA1 R.sup.2 and R.sup.3 are independent of one another and are identical or different and in each case represent hydrogen, halogen, alkyl, halogenoalkyl, alkoxy, alkylthio or alkoxycarbonyl, PA1 R.sup.2 and R.sup.3 together represent an alkylene chain having 3 to 6 carbon atoms which are linked via the ring positions 3 and 4 or 4 and 5, PA1 R.sup.4 represents hydrogen, halogen, alkyl, halogenoalkyl, hydroxyl, alkoxy, mercapto, alkylthio, amino or (di)alkylamino, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- to 7-membered, saturated or unsaturated ring which optionally contains a further hetero atom and which is optionally substituted by 1 or 2 alkyl groups; or PA1 R.sup.4 represents alkenyloxy or alkynyloxy, PA1 R.sup.5 represents hydrogen or alkyl and PA1 Ar represents unsubstituted or substituted aryl, are obtained by one of the processes described below. PA1 X represents halogen, PA1 R.sup.4-1 represents mercapto, alkoxy, alkylthio, amino or (di)alkylamino, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- to 7-membered, saturated or unsaturated ring which optionally contains a further hetero atom and which is optionally substituted by 1 or 2 alkyl groups, or represents alkenyloxy or alkynyloxy, PA1 X represents halogen, PA1 R.sup.4-1 has the abovementioned meaning and PA1 M represents hydrogen, or represents an alkali metal cation, PA1 R.sup.4-2 represents hydrogen or alkyl, PA1 X represents halogen, are reacted with diester derivatives of the formula (IV) ##STR11## in which R.sup.4-2 has the abovementioned meaning and PA1 R.sup.6 represents methyl or ethyl, PA1 R.sup.4-3 represents hydrogen, alkyl or halogenoalkyl, are obtained when picolineamidine derivatives of the formula (V) ##STR13## in which R.sup.1, R.sup.2 and R.sup.3 have the abovementioned meanings, or their acid addition salts PA1 R.sup.4-3 represents hydrogen, alkyl or halogenoalkyl and PA1 E represents a leaving group, PA1 R.sup.4-3 represents hydrogen, alkyl or halogenoalkyl and PA1 R.sup.7 represents alkyl having 1 to 4 carbon atoms, PA1 R.sup.4-3 represents hydrogen, alkyl or halogenoalkyl, PA1 R.sup.4-3 represents hydrogen, alkyl or halogenoalkyl and PA1 R.sup.8 represents alkyl having 1 to 4 carbon atoms, PA1 halogen, cyano, nitro, hydroxyl, amino, mercapto, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, in each case straight-chain or branched alkoxy or alkylthio each of which has 1 to 6 carbon atoms, in each case straight-chain or branched halogenoalkylthio or halogenoalkoxy each of which has 1 to 6 carbon atoms and each of which has 1 to 13 identical or different halogen atoms, in each case straight-chain or branched alkenyl or alkynyl having 2 to 6 carbon atoms, in each case straight-chain or branched alkenyloxy or alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, phenyl, phenoxy, phenylthio, phenylalkylthio or phenylalkyloxy each of which has 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, phenyl substituents which may furthermore be mentioned being: PA1 (di)alkylamino having 1 to 6 carbon atoms in the respective straight-chain or branched alkyl moieties, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered saturated or unsaturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 alkyl groups having 1 or 2 carbon atoms, or furthermore phenylamino, hydrazino which is optionally monosubstituted or disubstituted by straight-chain or branched alkyl having 1 to 6 carbon atoms or by phenyl, or alkyl- or phenylcarbonylamino having 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, aminocarbonyl, (di)alkylaminocarbonyl having 1 to 6 carbon atoms in the respective straight-chain or branched alkyl moieties, where, in the case of dialkylaminocarbonyl, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered saturated or unsaturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 alkyl groups having 1 or 2 carbon atoms, or straight-chain or branched alkoxycarbonyl having 1 to 6 carbon atoms, or two adjacent phenyl substituents together represent alkanediyl having 1 to 6 carbon atoms which optionally contains one or more hetero atoms from the series comprising oxygen, sulphur and nitrogen. PA1 (di)alkylamino having 1 to 4 carbon atoms in the respective straight-chain or branched alkyl moieties, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered saturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 methyl groups; furthermore phenylamino, hydrazino which is optionally monosubstituted or disubstituted by straight-chain or branched alkyl having 1 to 4 carbon atoms or by phenyl, or alkyl- or phenylcarbonylamino having 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, aminocarbonyl, (di)alkylaminocarbonyl having 1 to 4 carbon atoms in the respective straight-chain or branched alkyl moieties, where, in the case of dialkylaminocarbonyl, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered saturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 methyl groups; and also straight-chain or branched alkoxycarbonyl having 1 to 4 carbon atoms, or two adjacent phenyl substituents together represent alkanediyl which has 1 to 4 carbon atoms and which optionally contains 1 or 2 hetero atoms from the series comprising oxygen, sulphur and nitrogen. PA1 fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, amino, mercapto, methyl, ethyl, n-propyl or i-propyl, n-butyl, s-butyl, i-butyl or t-butyl, trifluoromethyl, trichloromethyl, difluoromethyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, chlorodifluoromethylthio, vinyl, 2-propenyl, 2-propynyl, 2-propenyloxy, 2-propynyloxy, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, phenoxy, phenylthio, phenylmethoxy or phenylmethylthio, further phenyl substituents which may be mentioned being: PA1 methylamino, dimethylamino, ethylamino, diethylmino, pyrrolidino, piperidino, morpholino, thiomorpholino, N-methylpiperazino, 2,6-dimethylmorpholino, phenylamino, hydrazino, 2-methylhydrazo, 2,2-dimethylhydrazo, 2-phenylhydrazo, methylcarbonylamino, phenylcarbonylamino, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methoxycarbonyl or ethoxycarbonyl. PA1 R.sup.9 represents methyl or ethyl, at temperatures of from 50.degree. to 150.degree. C., if appropriate in the presence of a diluent, such as, for example, methanol, ethanol, dioxane, tetrahydrofuran, pyridine, N,N-dimethylformamide, water or a mixture of water and the diluents mentioned, and if appropriate in the presence of a base, such as, for example, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium methanolate, potassium methanolate, triethylamine or N,N-diethylaniline, to give the likewise new compounds of the formula (XI) ##STR198## in which R.sup.1, R.sup.2, R.sup.3, R.sup.5 and Ar have the abovementioned meanings, and the resulting compounds of the formula (XI) are halogenated with a halogenation reagent, such as, for example, thionyl chloride, phosgene, phosphoryl chloride, phosphorus pentachloride, phosphoryl bromide or phosphorus tribromide, at temperatures between 50.degree. C. and 150.degree. C., if appropriate after they have been isolated and if appropriate in the presence of a diluent, such as, for example, benzene, toluene or chlorobenzene (cf. EP-OS (European Published Specification) 259,139 and EP-OS (European Published Specification) 270,362).
or
Furthermore, it has been found that the new pyridinylpyrimidine derivatives of the formula (I) ##STR4## in which R.sup.1 represents hydrogen, halogen, alkoxy, alkylthio, halogenoalkyl, amino or dialkylamino, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- to 7-membered, saturated or unsaturated ring which optionally contains a further hetero atom and which is optionally substituted by 1 or 2 alkyl groups;
in which furthermore
or
A) Pyridinylpyrimidine derivatives of the formula (Ia) ##STR5## in which H R.sup.1, R.sup.2, R.sup.3, R.sup.5 and Ar have the abovementioned meanings, are obtained when halogen-substituted pyridinylpyrimidine derivatives of the formula (II) ##STR6## in which R.sup.1, R.sup.2, R.sup.3, R.sup.5 and Ar have the abovementioned meaning and
are dehalogenated in the presence of a catalyst and under hydrogen pressure, if appropriate in the presence of a solvent and if appropriate in the presence of a base,
B) pyridinylpyrimidine derivatives of the formula (Ib) ##STR7## in which R.sup.1, R.sup.2, R.sup.3, R.sup.5 and Ar have the abovementioned meanings and
are obtained when halogen-substituted pyridinylpyrimidine derivatives of the formula (II) ##STR8## in which R.sup.1, R.sup.2, R.sup.3, R.sup.5 and Ar have the abovementioned meanings and
are reacted with compounds of the formula (III) EQU R.sup.4-1 --M (III)
in which
if appropriate in the presence of a diluent and if appropriate in the presence of a base, or
C) pyridinylpyrimidine derivatives of the formula (Ic) ##STR9## in which R.sup.1, R.sup.2, R.sup.3, R.sup.5 and Ar have the abovementioned meanings and
are obtained when halogen-substituted pyridinylpyrimidine derivatives or the formula (II); ##STR10## in which R.sup.1, R.sup.2, R.sup.3, R.sup.5 and Ar have the abovementioned meanings and
if appropriate in the presence of a diluent and if appropriate in the presence of a base, and the resulting substituted pyridinylpyrimidines are hydrolyzed, if appropriate in the presence of a diluent and in the presence of a base, and the products are subsequently decarboxylated in the presence of an acid; or
D) the pyridinylpyrimidine derivatives of the formula (Id) ##STR12## in which R.sup.1, R.sup.2, R.sup.3, R.sup.5 and Ar have the abovementioned meanings and
.alpha.) are cyclized with aryl ketones of the formula (VI) ##STR14## in which R.sup.5 and Ar have the abovementioned meanings,
if appropriate in the presence of a diluent and if appropriate in the presence of a base, or
.beta.) are reacted with acetals of the formula (VII) ##STR15## in which R.sup.5 and Ar have the abovementioned meanings,
if appropriate in the presence of a diluent and if appropriate in the presence of a base,
.gamma.) are reacted with 1,3-dioxo derivatives of the formula (VIII) ##STR16## in which R.sup.5 and Ar have the abovementioned meanings and
if appropriate in the presence of a diluent and in the presence of a base, or
.delta.) are reacted with diacetals of the formula (IX) ##STR17## in which Ar and R.sup.5 have the abovementioned meanings,
if appropriate in the presence of a diluent.
Finally, it has been found that the new pyridinylpyrimidine derivatives of the formula (I) have a good action against plant diseases.
Surprisingly, the pyridinylpyrimidine derivatives of the general formula (I) according to the invention have a considerably more powerful fungicidal activity than the pyridinylpyrimidine derivatives known from the prior art, such as, for example, 2-(6-methyl-2-pyridinyl)-4-hydroxy-6-phenylpyrimidine, 2-(6-methyl-2-pyridinyl)-4-o-tolylpyrimidine or 2-(6-phenyl-2-pyridinyl)-4-chloro-6-methylpyrimidine, which are similar compounds chemically and from the point of view of their action.
Preferred substituents or areas of the radicals mentioned in the formulae given above and below are illustrated in the following:
The term alkyl in the definitions of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 in the general formulae represents straight-chain or branched alkyl having preferably 1 to 6, particularly preferably 1 to 4 and in particular 1 or 2, carbon atoms. The following may be mentioned by way of example: methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, n-pentyl and t-pentyl. The term alkenyloxy in the definition of R.sup.4 in the general formulae represents straight-chain or branched alkenyloxy having preferably 2 to 6, particularly preferably 2 to 4 and very particularly preferably 2 or 3, carbon atoms. The following may be mentioned by way of example: vinyloxy, allyloxy, 2-propenyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy and 1-methallyloxy.
The term alkynyloxy in the definition of R.sup.4 in the general formulae represents straight-chain or branched alkynyloxy having preferably 2 to 6, particularly preferably 2 to 4 and very particularly preferably 2 or 3, carbon atoms. The following may be mentioned by way of example: 2-propynyloxy, 1-butynyloxy, 2-butynyloxy and 3-butynyloxy.
The term (di)alkylamino in the definitions of R.sup.1 and R.sup.4 in the general formulae represents an amino group having 1 or 2 alkyl groups, each of which can be straight-chain or branched and identical or different and each of which preferably contains 1 to 6, in particular 1 to 4 carbon atoms, of which groups methyl, ethyl, n- and i-propyl may be mentioned. The following may be mentioned by way of example: methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, i-propylamino and di-i-propylamino.
If, in the case of dialkylamino, the two radicals together with the nitrogen atom to which they are bonded form a ring, the latter contains 5 to 7, preferably 5 or 6, ring members. The ring can contain 1 to 3 double bonds, but it is preferably saturated. The ring can contain a further hetero atom, preferably oxygen, sulphur or nitrogen, and it can be substituted by 1 or 2 alkyl groups, preferably by one alkyl group. The following may be mentioned by way of example: pyrrolidino, piperidino, morpholino, N-methylpiperazino, thiomorpholino and 2,6-dimethylmorpholino.
The term unsubstituted or substituted aryl in the definition of Ar in the general formulae is understood as meaning aryl having preferably 6 to 10 carbon atoms in the aryl moiety. The following may be mentioned by way of example and as preferred: unsubstituted or substituted phenyl or naphthyl, in particular phenyl.
The term halogenoalkyl in the definitions of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in the general formulae preferably represents straight-chain or branched alkyl having in each case 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, and in each case 1 to 13, preferably 1 to 6, identical or different halogen atoms, as defined under halogen; the following may be mentioned by way of example and as preferred: fluoromethyl, chloromethyl, bromomethyl, fluoroethyl, chloroethyl, bromoethyl, fluoro-n-propyl, chloro-n-propyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, difluoroethyl, trifluoroethyl, trichloroethyl, chlorodifluoromethyl, trifluorochloroethyl, chlorobutyl and fluorobutyl.
The term alkoxy in the definitions of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in the general formulae is understood as meaning straight-chain or branched alkoxy having preferably 1 to 6, in particular 1 to 4, carbon atoms. The following may be mentioned by way of example: methoxy, ethoxy, propoxy, butoxy, as well as their isomers, i-propoxy, i-, s- and t-butoxy.
The term alkylthio in the definitions of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in the general formulae is understood as meaning straight-chain or branched alkylthio having preferably 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms. The following may be mentioned by way of example: methylthio-, ethylthio-, propylthio-, butylthio-, pentylthio as well as their isomers, such as, for example, i-propylthio and i-, s- and t-butylthio. The following are particularly preferred: methylthio, ethylthio, tetrafluoroethylthio, trichloroethylthio, chlorodifluoromethylthio and trifluorochloroethylthio.
The term alkoxycarbonyl in the definitions of R.sup.2 and R.sup.3 in the general formulae is understood as meaning straight-chain or branched alkoxycarbonyl having 1 to 6, preferably 1 to 4, carbon atoms in the alkoxy radical. The following may be mentioned by way of example: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-, i-, s- and t-butoxycarbonyl.
Unsubstituted or substituted aryloxy and arylthio in the definition of R.sup.1 in the general formulae generally represents aryl having preferably 6 to 10 carbon atoms in the aryl moiety. The following may be mentioned by way of example: unsubstituted or substituted phenoxy or phenylthio.
In general, unsubstituted or substituted aralkyloxy or aralkylthio in the definition of R.sup.1 preferably contain 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety and preferably phenyl as the aryl moiety. Aralkyloxy or aralkylthio groups which may be mentioned by way of example are benzyloxy and benzylthio.
Halogen in the definitions of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in the general formulae represents fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
The substituents of the aryl radicals as such or in combinations such as aryloxy, arylthio, aralkyloxy and aralkylthio have the meanings indicated below.
Halogen as a substituent generally represents fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, particularly preferably fluorine and chlorine.
Alkyl as a substituent or in combinations such as phenylalkylthio or phenylalkyloxy generally represents straight-chain or branched alkyl, preferably having 1 to 6, particularly preferably having 1 to 4, carbon atoms, methyl and ethyl being very particularly preferred. The enumeration by way of example corresponds to that given hereinabove.
Alkoxy as a substituent generally represents straight-chain or branched alkoxy having 1 to 6, particularly preferably to 4, carbon atoms per alkyl radical; the following may be mentioned by way of example and as being preferred: methoxy, ethoxy, n- and i- propoxy, n-, i-, s- and t-butoxy, n-hexoxy and i-hexoxy
Alkylthio as a substituent in the radicals generally represents straight-chain or, branched alkylthio having preferably 1 to 6 carbon atoms, for example it is understood as meaning the following groups: methylthio, ethylthio, propylthio, butylthio, pentylthio as well as their isomers, such as, for example, i-propylthio, i-, s- and t-butylthio, 1-methyl-butylthio, 2-methyl-butylthio- and 2-methyl-butylthio. Preferred alkylthio radicals contain 1 to 4 carbon atoms. The following are particularly preferred: methylthio, ethylthio, n-, i-, s- propylthio and n-, i-, s- and t-butylthio.
Alkoxycarbonyl as a substituent in the radicals generally represents straight-chain or branched alkoxycarbonyl having 1 to 6, preferably 1 to 4, carbon atoms in the alkoxy radical; the following may be mentioned by way of example: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-, i-, s- and t-butoxycarbonyl.
Cycloalkyl as a substituent in the radicals generally represents cycloalkyl having preferably 3 to 7, in particular 3, 5 or 6, carbon atoms. The following may be mentioned by way of example: unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
Alkenyl and alkynyl as substituents in the radicals generally represent straight-chain or branched alkenyl or alkynyl having preferably 2 to 6, particularly preferably 2 to 4 and very particularly preferably 2 or 3, carbon atoms. The following may be mentioned by way of example: vinyl, allyl, prop-2-enyl, 1-butenyl, 2-butenyl, 3-butenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl and 3-butynyl.
Akenyloxy and alkynyloxy as substituents in the radicals generally represent straight-chain or branched alkenyloxy or alkynyloxy having preferably 2 to 6, particularly preferably 2 to 4 and very particularly preferably 3, carbon atoms. The following may be mentioned by way of example: alkyloxy, 2-propenyloxy, 2-butenyloxy, 2-propynyloxy and 2-butynyloxy.
Halogenoalkyl and halogenoalkoxy as substituents in the radicals generally represent straight-chain or branched halogenoalkyl or halogenoalkoxy having in each case 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, and in each case 1 to 13, preferably 1 to 9, identical or different halogen atoms as defined under halogen; the following may be mentioned by way of example: fluoromethyl, chloromethyl, bromomethyl, fluoroethyl, chloroethyl, bromoethyl, fluoro-n-propyl, chloro-n-propyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, difluoroethyl, trifluoroethyl, trichloroethyl, chloro-difluoro-methyl, trifluorochloroethyl, chlorobutyl, fluorobutyl, fluoromethoxy, chloromethoxy, bromomethoxy, fluoroethoxy, chloroethoxy, bromoethoxy, fluoropropoxy, chloropropoxy, bromopropoxy, fluorobutoxy, chlorobutoxy, fluoro-i-propoxy, chloro-i-propoxy, difluoromethoxy, trifluoromethoxy, dichloromethoxy, trichloromethoxy, difluoroethoxy, trifluoroethoxy, tetrafluoroethoxy, trichloroethoxy, chlorodifluoromethoxy and trifluorochloroethoxy.
Halogenoalkylthio as a substituent in the radicals generally represents straight-chain or branched halogenoalkylthio in each case having 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, and in each case 1 to 13, preferably 1 to 9, identical or different halogen atoms as defined under halogen; the following may be mentioned by way of example: fluoromethylthio, chloromethylthio, bromomethylthio, fluoroethylthio, chloroethylthio, bromoethylthio, fluoropropylthio, chloropropylthio, bromopropylthio, fluorobutylthio, chlorobutylthio, bromobutylthio, fluoro-i-propylthio, chloro-i-propylthio, difluoromethylthio, trifluoromethylthio, dichloromethylthio, trichloromethylthio, difluoroethylthio, trifluoroethylthio, tetrafluoroethylthio, trichloroethylthio, chlorodifluoromethylthio and trifluorochloroethylthio.
(Di)alkylamino as a substituent in the radicals generally represents an amino group having 1 or 2 alkyl groups, each of which can be straight-chain or branched and identical or different, and each of which preferably contains 1 to 6, in particular 1 to 4, carbon atoms, of which groups methyl, ethyl, and n- and i-propyl may be mentioned. Examples which may be given are methylamino, ethylamino, n-propylamino, i-propylamino, dimethylamino, diethylamino, di-n-propylamino and di-i-propylamino.
If, in the case of dialkylamino, the two radicals together with the nitrogen atom to which they are bonded form a ring, the latter contains 5 to 7, preferably 5 or 6, ring members. The ring can contain 1 to 3 double bonds, but it is preferably saturated. The ring can contain a further hetero atom, preferably oxygen, sulphur or nitrogen, and it can be substituted by 1 or 2 alkyl groups, preferably by one alkyl group. The following may be mentioned by way of example: pyrrolidino, piperidino, morpholino, N-methylpiperazino, thiomorpholino and 2,6-dimethylmorpholino.
(Di)alkylaminocarbonyl as a substituent in the radicals generally represents an aminocarbonyl group having 1 or 2 alkyl groups, each of which can be straight-chain or branched and identical or different, and each of which preferably contains 1 to 6, in particular 1 to 4, carbon atoms, of which groups methyl, ethyl, and n- and i-propyl may be mentioned. The following may be mentioned by way of example: methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl and diethylaminocarbonyl.
If, in the case of dialkylamino, the two radicals together with the nitrogen atom to which they are bonded form a ring, the latter contains 5 to 7, preferably 5 or 6, ring members. The ring can contain 1 to 3 double bonds, but it is preferably saturated. The ring can contain a further hetero atom, preferably oxygen, sulphur or nitrogen, and it can be substituted by 1 or 2 alkyl groups, preferably by one alkyl group. The following may be mentioned by way of example: pyrrolidino, piperidino, morpholino, n-methylpiperazino, thiomorpholino and 2,6-dimethylmorpholino.
Alkylcarbonylamino as a substituent in the radicals generally represents straight-chain or branched alkylcarbonylamino having 1 to 6, preferably 1 to 4, carbon atoms in the alkyl radical; the following may be mentioned by way of example: methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, i-propylcarbonylamino.
Alkylhydrazo as a substituent in the radicals generally represents straight-chain or branched alkylhydrazo having 1 to 6, preferably 1 to 4, carbon atoms in the alkyl moiety. The following may be mentioned by way of example: 2-methylhydrazo, 2-ethylhydrazo, 2-propylhydrazo and 2,2-dimethylhydrazo.
Formula (I) provides a general definition of the pyridinylpyrimidine derivatives according to the invention. Preferred compounds of the formula (I) are those in which
R.sup.1 represents hydrogen, halogen, in each case straight-chain or branched alkoxy or alkylthio each of which has 1 to 6 carbon atoms, or represents straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, amino, alkylamino or dialkylamino each of which has 1 to 6 carbon atoms in the respective straight-chain or branched alkyl moieties, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered saturated or unsaturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 alkyl groups having 1 or 2 carbon atoms; or furthermore represents phenoxy or phenylthio, each of which is optionally monosubstituted or polysubstituted by identical or different substituents, phenyl substituents which may be mentioned being: halogen, cyano, nitro, alkyl, alkoxy or alkylthio each of which has 1 or 2 carbon atoms, and also halogenoalkyl, halogenoalkoxy or halogenoalkylthio each of which has 1 or 2 carbon atoms and each of which has 1 to 5 fluorine and/or chlorine atoms, or R.sup.1 represents phenylalkoxy or phenylalkylthio each of which has 1 to 4 carbon atoms in the respective straight-chain or branched alkyl moiety and each of which is optionally monosubstituted or polysubstituted by identical or different substituents, suitable substituents of the phenyl moiety being the abovementioned phenyl substituents, PA0 R.sup.2 and R.sup.3 are independent of one another and identical or different and in each case represent hydrogen, halogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, or represent straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or represent in each case straight-chain or branched alkoxy or alkylthio each of which has 1 to 6 carbon atoms, or represent straight-chain or branched alkoxycarbonyl having 1 to 6 carbon atoms in the alkoxy moiety, or PA0 R.sup.2 and R.sup.3 together represent an alkyl chain which has 3 to 5 carbon atoms and which is linked via the ring positions 3 and 4 or 4 and 5, PA0 R.sup.4 represents hydrogen, halogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, hydroxyl, mercapto, in each case straight-chain or branched alkoxy or alkylthio each of which has 1 to 6 carbon atoms, amino, alkylamino or dialkylamino each of which has 1 to 6 carbon atoms in the respective straight-chain or branched alkyl moieties, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered saturated or unsaturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 alkyl groups having 1 or 2 carbon atoms, or represents in each case straight-chain or branched alkenyloxy or alkynyloxy each of which has 2 to 6 carbon atoms, PA0 R.sup.5 represents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms, and PA0 Ar represents phenyl which is optionally mono-substituted or polysubstituted by identical or different substituents, substituents which may be mentioned being: PA0 R.sup.1 represents hydrogen, fluorine, chlorine, bromine, in each case straight-chain or branched alkoxy or alkylthio each of which has 1 to 4 carbon atoms, or represents straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 fluorine and/or chlorine atoms, or amino, alkylamino or dialkylamino each of which has 1 to 4 carbon atoms in the respective straight-chain or branched alkyl moieties, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered saturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 methyl groups, furthermore represents phenoxy or phenylthio each of which is optionally monosubstituted or disubstituted by identical or different substituents, suitable phenyl substituents which may be mentioned being: fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio or trifluoromethylthio, or R.sup.1 represents phenylalkoxy phenylalkylthio each of which has 1 or 2 carbon atoms in the alkyl moiety and each of which is optionally monosubstituted or disubstituted by identical or different substituents, suitable substituents of the phenyl moiety being the above-mentioned phenyl substituents. PA0 R.sup.2 represents hydrogen, fluorine, chlorine or bromine, or represents straight-chain or branched alkyl, having 1 to 4 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 fluorine and/or chlorine atoms, or represents in each case straight-chain or branched alkoxy or alkylthio having 1 to 4 carbon atoms, or represents straight-chain or branched alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, PA0 R.sup.3 represents hydrogen, fluorine, chlorine, bromine or straight-chain or branched alkyl having 1 to 4 carbon atoms or PA0 R.sup.2 and R.sup.3 together represent an alkyl chain which has 3 or 4 carbon atoms and which is linked via the ring positions 3 and 4 or 4 and 5, PA0 R.sup.4 represents hydrogen, fluorine, chlorine, bromine, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 fluorine and/or chlorine atoms, hydroxyl, mercapto, in each case straight-chain or branched alkoxy or alkylthio having 1 to 4 carbon atoms, amino, alkylamino or dialkylamino each of which has 1 to 4 carbon atoms in the respective straight-chain or branched alkyl moieties, where, in the case of dialkylamino, the two radicals may, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered saturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 methyl groups, or represents in each case straight-chain or branched alkenyloxy or alkynyloxy each of which has 3 or 4 carbon atoms, PA0 R.sup.5 represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms and PA0 Ar represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, substituents which may be mentioned being: fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, mercapto, amino, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 fluorine and/or chlorine atoms, in each case straight-chain or branched alkoxy or alkylthio each of which has 1 to 4 carbon atoms, in each case straight-chain or branched halogenoalkoxy or halogenoalkylthio each of which has 1 to 4 carbon atoms and each of which has 1 to 9 fluorine and/or chlorine atoms, in each case straight-chain or branched alkenyl or alkynyl each of which has 2 to 4 carbon atoms, in each case straight-chain or branched alkenyloxy or alkinyloxy each of which has 3 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio each of which has or 2 carbon atoms in the alkyl moiety; phenyl substituents which may furthermore be mentioned being: PA0 R.sup.1 represents hydrogen, fluorine, chlorine, methoxy, ethoxy, n-propoxy or i-propoxy, methylthio, ethylthio, trifluoromethyl, trichloromethyl, difluoromethyl or chlorofluoromethyl, or represents methylamino, dimethylamino, ethylamino, diethylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, n-methyl-piperazino, 2,6-dimethylmorpholino, or represents phenoxy, phenylthio, benzyloxy or benzylthio, PA0 R.sup.2 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl or i-propyl, or represents trifluoromethyl, trichloromethyl, difluoromethyl, dichloromethyl, or represents methoxy or ethoxy, or represents methylthio, or represents methoxy- or ethoxycarbonyl, PA0 R.sup.3 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl or t-butyl, PA0 R.sup.4 represents hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, trichloromethyl, hydroxyl, mercapto, methoxy, ethoxy, n-propoxy, i-propoxy, methylthio, ethylthio, n-propylthio or i-propylthio, n-butylthio, i-butylthio, s -butylthio or t-butylthio, or represents amino, methylamino, ethylamino, dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, N-methylpiperazino or 2,6-dimethylmorpholino, or represents 2-propenyloxy or 2-propynyloxy, PA0 R.sup.5 represents hydrogen, methyl, ethyl, n-propyl, i-propyl or n-butyl and PA0 E preferably represents halogen, in particular chlorine, bromine or iodine, or represents dialkylamino, such as, for example, dimethylamino, or represents in each case optionally substituted alkylsulphonyloxy, alkoxysulphonyloxy or arylsulphonyloxy, such as, for example, methanesulphonyloxy, trifluoromethanesulphonyloxy, methoxysulphonyloxy, ethoxysulphonyloxy or p-toluenesulphonyloxy. PA0 R.sup.8 preferably represents methyl or ethyl. PA0 Pythium species, such as, for example, Pythium ultimum; PA0 Phytophthora species, such as, for example, Phytophthora infestans; PA0 Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; PA0 Plasmopara species, such as, for example, Plasmopara viticola; PA0 Peronospora species, such as, for example, Peronospora pisi or P. brassicae; PA0 Eyrsiphe species, such as, for example, Erysiphe graminis; PA0 Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; PA0 Podosphaera species, such as, for example, Podosphaera leucotricha; PA0 Venturia species, such as, for example, Venturia, inaequalis; PA0 Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, syn: Helminthosporium); PA0 Cochliobolus species, such as, for example, Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium); PA0 Uromyces species, such as, for example, Uromyces appendiulatus; PA0 Puccinia species, such as, for example, Puccinia recondita; PA0 Tilletia species, such as, for example, Tilletia caries; PA0 Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; PA0 Pellicularia species, such as, for example, Pellicularia sasakii; PA0 Pyricularia species, such as, for example, Pyricularia cryzae; PA0 Fusarium species, such as, for example, Fusarium culmorum; PA0 Botrytis species, such as, for example, Botrytis cinerea; PA0 Septoria species, such as, for example, Septoria nodorum; PA0 Leptosphaeria species, such as, for example, Leptosphaeria nodorum; PA0 Cercospora species, such as, for example, Cercospora canescens; PA0 Alternaria species, such as, for example, Alternaria brassicae and PA0 Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
Particularly preferred compounds of the formula (I) are those in which
Very particularly preferred compounds of the formula (I) are those in which
Ar represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, substituents which may be mentioned being:
The following pyridinylpyrimidine derivatives of the general formula (I) may be mentioned individually in addition to the compounds mentioned in the preparation examples: ##STR18##
TABLE 1 __________________________________________________________________________ R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 Ar __________________________________________________________________________ Cl H H CH.sub.3 O CH.sub.3 Cl H H C.sub.2 H.sub.5 O H ##STR19## Cl H H OCH.sub.2CHCH.sub.2 H ##STR20## Cl 5-Cl H OCH.sub.2CCH H ##STR21## Cl 4-Cl H CH.sub.3 H ##STR22## Cl 5-Cl 3-Cl H CH.sub.3 ##STR23## Br H H Br C.sub.2 H.sub.5 ##STR24## Br H H OH CH.sub.3 ##STR25## Br 5-CF.sub.3 H H H ##STR26## Br H 3-CO.sub.2 CH.sub.3 CF.sub.3 H ##STR27## F 4-F H SCH.sub.3 H ##STR28## F 5-SCH.sub.3 H NHCH.sub.3 H ##STR29## CH.sub.3 O H H N(CH.sub.3).sub.2 H ##STR30## CH.sub.3 O H 3-CH.sub.3 NH.sub.2 H ##STR31## CH.sub.3 O 5-C.sub.2 H.sub.5 H SH H ##STR32## CH.sub.3 O H H Cl H ##STR33## C.sub.2 H.sub.5 O 4-C.sub.2 H.sub.5 O H Cl H ##STR34## C.sub.2 H.sub.5 O 4-Cl H F H ##STR35## n-C.sub.3 H.sub.7 O H H CH.sub.3 O H ##STR36## SCH.sub.3 H H C.sub.2 H.sub.5 O H ##STR37## SC.sub.2 H.sub.5 H H CF.sub.3 H ##STR38## N(CH.sub.3).sub.2 H H CCl.sub.3 H ##STR39## CF.sub.3 H H n-C.sub.3 H.sub.7 O H ##STR40## CF.sub.3 H 3-OCH.sub.3 OH H ##STR41## CHF.sub.2 H H CH.sub.3 CH.sub.3 ##STR42## CCl.sub.3 H H H C.sub.2 H.sub.5 ##STR43## CHClF H 3-Cl CH.sub.3 S H ##STR44## H 5-CH.sub.3 O 3-CH.sub.3 O SH H ##STR45## ##STR46## H H NH.sub.2 H ##STR47## ##STR48## H H CH.sub.3 O H ##STR49## ##STR50## H H CH.sub.3 O CH.sub.3 ##STR51## ##STR52## H H C.sub.2 H.sub.5 O H ##STR53## ##STR54## H H Cl H ##STR55## ##STR56## H 3-CF.sub.3 Cl H ##STR57## H 5-Cl 4-Cl H H ##STR58## H 5-Cl 3-Cl H H ##STR59## H H 3-Br H H ##STR60## H H 3-CH.sub.3 CH.sub.3 H ##STR61## H H 3-CO.sub.2C.sub.2 H.sub.5 CH.sub.3 H ##STR62## H 5-CO.sub.2CH.sub.3 H H H ##STR63## H 5-CF.sub.3 H OH H ##STR64## Cl 5-CF.sub.3 H OH H ##STR65## CH.sub.3 O 5-CF.sub.3 H Cl H ##STR66## Br 5-CHF.sub.2 H Cl H ##STR67## Cl 5-CCl.sub.3 H Cl H ##STR68## CH.sub.3 O 5-CCl.sub.3 H Br H ##STR69## F 5-CHClF H H CH.sub.3 ##STR70## CH.sub.3 S 5-CH.sub.3 H H CH.sub.3 ##STR71## H 5-C.sub.2 H.sub.5 H H H ##STR72## H 5-Cl H H H ##STR73## Cl 5-Cl H H C.sub.2 H.sub.5 ##STR74## N(CH.sub.3).sub.2 5-Cl H H H ##STR75## ##STR76## 5-Cl H H H ##STR77## ##STR78## 5-Br H H H ##STR79## ##STR80## 5-Br H CH.sub.3 H ##STR81## ##STR82## 5-Br H CH.sub.3 O H ##STR83## H 5-CH.sub.3 O H CH.sub.3 O C.sub.3 H.sub.7 -n ##STR84## CF.sub.3 5-C.sub.2 H.sub.5 O H OH H ##STR85## H H 4-Br H H ##STR86## H H 4-Br CH.sub.3 H ##STR87## H H 4-Cl CH.sub.3 O H ##STR88## H H 4-Cl CH.sub.3 O H ##STR89## H H 4-CF.sub.3 CH.sub.3 O H ##STR90## H H 4-CHF.sub.2 n-C.sub.3 H.sub.7 S H ##STR91## H H 4-CHCl.sub.2 CH.sub.2CHCH.sub.2 O H ##STR92## H 5-F 4-CH.sub.3 n-C.sub.3 H.sub.7 O H ##STR93## H 5-CH.sub.3 4-CH.sub.3 i-C.sub.3 H.sub.7 O H ##STR94## H H 3-C.sub.2 H.sub.5 CHCCH.sub.2 O H ##STR95## H H 3-OCH.sub.3 CH.sub.3 S H ##STR96## H H 3-OCH.sub.3 CH.sub.3 CN H ##STR97## H H 3-OC.sub.2 H.sub.5 (CH.sub.3).sub.2 N H ##STR98## H H 3-C.sub.3 H.sub.7 n CH.sub.3 O H ##STR99## H H 3-CF.sub.3 CH.sub.3 O CH.sub.3 ##STR100## H H 3-CF.sub.3 CH.sub.3 O C.sub.2 H.sub.5 ##STR101## H H 3-CCl.sub.3 C.sub.2 H.sub.5 O H ##STR102## H H 3-CO.sub.2CH.sub.3 SH H ##STR103## H H 3-CO.sub.2C.sub.2 H.sub.5 C.sub.2 H.sub.5 O H ##STR104## H H 3-F CH.sub.2CHCH.sub.2 O H ##STR105## H 5-Cl 3-Cl H CH.sub.3 ##STR106## H 5-Br 3-Br H H ##STR107## H 5-CCl.sub.3 3-Cl H H ##STR108## H 5-CO.sub.2CH.sub.3 3-C.sub.2 H.sub.5 O OH H ##STR109## H H H OH H ##STR110## H H H Cl H ##STR111## H H H Cl H ##STR112## H H H Br H ##STR113## Cl H H F H ##STR114## Cl H H H C.sub.3 H.sub.7 -n ##STR115## Cl H H H H ##STR116## Cl H H H H ##STR117## Br H H H CH.sub.3 ##STR118## Br H H CH.sub.3 O H ##STR119## CH.sub.3 O H H H H ##STR120## CH.sub.3 O H H H H ##STR121## C.sub.2 H.sub.5 O H H H H ##STR122## n-C.sub.3 H.sub.7 O H H OH OH ##STR123## i-C.sub.3 H.sub.7 O H H SH H ##STR124## CF.sub.3 H H NH.sub.2 H ##STR125## CH.sub.3 S H H H C.sub.2 H.sub.5 ##STR126## CH.sub.3 S H H CH.sub.3 H ##STR127## C.sub.2 H.sub.5 S H H H H ##STR128## C.sub.2 H.sub.5 S H H H H ##STR129## (CH.sub.3).sub.2 N H H H H ##STR130## (C.sub.2 H.sub.5).sub.2 N H H H H ##STR131## CCl.sub.3 H H Cl H ##STR132## CHF.sub.2 H H H H ##STR133## ##STR134## H H H H ##STR135## ##STR136## H H H CH.sub.3 ##STR137## ##STR138## H H OH H ##STR139## ##STR140## H H OH H ##STR141## ##STR142## H H Cl H ##STR143## ##STR144## H H CH.sub.3 O H ##STR145## ##STR146## H H OH C.sub.2 H.sub.5 ##STR147## ##STR148## H H CH.sub.3 O H ##STR149## ##STR150## H H CH.sub.3 S H ##STR151## ##STR152## H H Cl H ##STR153## ##STR154## H H F H ##STR155## ##STR156## H H H H ##STR157## ##STR158## H H H H ##STR159## F H H H n-C.sub.3 H.sub.7 ##STR160## F H H CH.sub.3 H ##STR161## Cl H H C.sub.2 H.sub.5 O H ##STR162## Br H H CH.sub.2CHCH.sub.2 O H ##STR163## H H H i-C.sub.3 H.sub.7 O H ##STR164## ##STR165## H H H H ##STR166## ##STR167## H H H CH.sub.3 ##STR168## H 4,5-(CH.sub.2).sub.4 H H ##STR169## H H 3-CHCl.sub.2 CH.sub.3 H ##STR170## ##STR171## H H H C.sub.2 H.sub.5 ##STR172## H 3-CHF.sub.2 H CH.sub.3 S H ##STR173## ##STR174## 3,4-(CH.sub.2).sub.4 CH.sub.3 O H ##STR175## ##STR176## H H C.sub.2 H.sub.5 S H ##STR177## H 4-C.sub.2 H.sub.5 H i-C.sub.3 H.sub.7 S H ##STR178## H 4,5-(CH.sub.2).sub.3 H CH.sub.3 ##STR179## H 5-CH.sub.3 3-CH.sub.3 H H ##STR180## ##STR181## H H CH.sub.3 H ##STR182## ##STR183## H 3-CH.sub.3 t-C.sub.4 H.sub.9 S H ##STR184## (C.sub.2 H.sub.5).sub.2 N H H F H ##STR185## H 5-F 3-F CH.sub.3 CH.sub. 3 ##STR186## ##STR187## H n-C.sub.3 H.sub.7 Br H ##STR188## __________________________________________________________________________
If, for example, 4-chloro-2-(2-pyridyl)-6-(4-fluoro-phenyl)-pyrimidine is used as starting substance and hydrogen and palladium/carbon as catalyst, process (A) according to the invention may be described by the following equation ##STR189##
If, for example, 4-chloro-2-(2-pyridyl)-6-(4-fluoro-phenyl)-pyrimidine and sodium methanolate are used as starting substances, process (B) according to the invention can be described by the following equation: ##STR190##
If, for example, 4-chloro-2-(2-pyridyl)-6-(4-fluoro-phenyl)-pyrimidine and diethyl malonate are used, process (C) according to the invention may be represented by the following equation: ##STR191##
If, for example, 2-pyridinyl-amidine hydrochloride and 1-(4-cyclohexyl-phenyl)-3-dimethylaminopropen-1-one and sodium methylate are used as starting substances, process (D-.alpha.) according to the invention may be represented by the following equation: ##STR192##
If, for example, 2-pyridinyl-amidine hydrochloride and 1-phenyl-3,3-dimethoxy-propan-1-one are used, process (D-.beta.) according to the invention may be described by the following equation: ##STR193##
If, for example, 2-pyridinyl-amidine hydrochloride and 1-phenyl-1,3-butanedione are used as starting substances, process (D-.gamma.) according to the invention may be described by the following equation: ##STR194##
If, for example, 2-pyridinyl-amidine hydrochloride and 1,1,3,3-tetramethoxypropyl-benzene are used, process (D-.delta.) according to the invention may be described by the following equation: ##STR195##
Formula (II) provides a general definition of the halogen-substituted pyridinylpyrimidine derivatives required as starting substances for carrying out processes (A), (B) and (C) according to the invention. In this formula (II), R.sup.1, R.sup.2, R.sup.3, R.sup.5, Ar and X represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.
The compounds of the formula (II) are new. However, they can obtained in analogous manner by known processes, for example by a process in which picolineamine derivatives of the formula (V) ##STR196## in which R.sup.1, R.sup.2 and R.sup.3 have the abovementioned meanings, their acid addition salts,
are cyclized with benzoyl acetic ester derivatives of the formula (X) ##STR197## in which Ar and R.sup.5 have the abovementioned meanings and
The picolineamine derivatives of the formula (V) or their acid addition salts are known in some cases and/or can be prepared in analogy to known processes (cf. EP-OS (European Published Specification) 259,139 and EP-OS (European Published Specification) 270,362).
Formula (III) provides a general definition of the compounds furthermore required as starting substances for carrying out process (B) according to the invention. In this formula (III), R.sup.4-1 and M preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.
The compounds of the formula (III) are generally known compounds of organic chemistry.
Formula (IV) provides a general definition of the diester derivatives furthermore required as starting substances for carrying out process (C) according to the invention. In this formula (IV), R.sup.4-2 and R.sup.6 preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.
The compounds of the formula (IV) are generally known compounds of organic chemistry.
Formula (VI) provides a general definition of the aryl ketones furthermore required as starting substances for carrying out process (D-.alpha.) according to the invention. In this formula (VI), R.sup.4-3, R.sup.5 and Ar represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.
The compounds of the formulae (VI) are generally known compounds of organic chemistry.
Formula (VII) provides a general definition of the acetals furthermore required as starting substances for carrying out process (D-.beta.) according to the invention. In this formula (VII), Ar, A.sup.4-3 and R.sup.5 represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.
R7 preferably represents methyl or ethyl.
Formula (VIII) provides a general definition of the 1,3-dioxo derivatives furthermore required for carrying out process (D-.gamma.) according to the invention. In this formula (VIII), Ar, R.sup.4-3 and R.sup.5 represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.
The compounds of the formula (VII) and (VIII) are generally known compounds of organic chemistry.
Formula (IX) provides a general definition of the diacetals furthermore required as starting substances for carrying out process (D-.delta.) according to the invention. In this formula (IX), Ar, R.sup.4-3 represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.
The compounds of the formula (IX) are generally known compounds of organic chemistry.
Process (A) according to the invention for the preparation of the new compounds of the formula (Ia) is preferably carried out using diluents. Diluents which are suitable for this purpose are virtually all inert organic solvents. These include benzene, toluene, xylene, tetrahydrofuran and dioxane, esters, such as methyl acetate and ethyl acetate, alcohols, such as methanol, ethanol and isopropanol, and also water. Preferably used diluents are water, methanol, ethanol, ethyl acetate and toluene, or mixtures of these diluents.
When carrying out process (A) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0.degree. C. and +100.degree. C., preferably at temperatures between +20 C and +50.degree. C.
Process (A) according to the invention is preferably carried out using catalysts. Suitable catalysts are customary hydrogenation catalysts, such as, for example, Raney nickel, elementary platinum or palladium, but palladium/active carbon is preferably used.
Process (A) according to the invention is carried out in the presence of bases. Examples of suitable bases are alkali metal hydroxides, such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, such as, for example, calcium hydroxide, alkali metal carbonates, alkali metal acetates and alkali metal alcoholates, such as sodium carbonate, potassium carbonate, sodium methylate, potassium methylate, sodium ethylate and potassium ethylate, ammonia, amines, such as diethylamine, or basic ion exchangers.
Process (A) according to the invention is generally carried out at a hydrogen pressure of 1 to 5 atmospheres, preferably at 1 to 3 atmospheres. For working up, the catalyst is filtered off, water is added to the reaction solution, and the mixture is extracted with an organic solvent. Further working-up is carried out by customary methods.
For carrying out process (A) according to the invention, 1 to 10 moles, preferably 1 to 5 moles, of hydrogen and 0.01 to 1 mole, preferably 0.01 to 0.1 mole, of catalyst are generally employed per mole of halogenated pyridinylpyrimidine derivative of the formula (II).
Process (B) according to the invention for the preparation of the new compounds of the formula (Ib) is preferably carried out using diluents. Suitable diluents for this purpose are virtually all inert organic solvents. These include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, alcohols, such as methanol, ethanol or isopropanol. Preferably used diluents are ethers, such as diethyl ether, dioxane and tetrahydrofuran, and alcohols such as methanol and ethanol, or mixtures of these diluents.
When carrying out process (B) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0.degree. C. and +150.degree. C., preferably at temperatures between +10.degree. C. and +120.degree. C.
Process (B) according to the invention is carried out in the presence of bases. Preferably used bases are alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, or organic bases, such as sodium methanolate, triethylamine or pyridine.
For carrying out process (B) according to the invention, 1 to 3 moles, preferably 1 to 1.5 moles, of compound of the formula (III) are generally employed per mole of halogen-substituted pyridinylpyrimidine derivative of the formula (II).
For carrying out process (B) according to the invention, the reaction mixture is stirred for several hours at the required temperature. Working-up is carried out by customary methods, and, if appropriate, the product is subsequently purified by chromatography.
Process (C) according to the invention for the preparation of the new compounds of the formula (Ic) is preferably carried out using diluents. Suitable diluents for this purpose are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as, for example, acetonitrile and propionitrile, dimethyl sulphoxide and sulpholane, and mixtures of these diluents.
When carrying out the first reaction step of process (C) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between -10.degree. C. and +180.degree. C., preferably at temperatures between 0.degree. C. and +150 C.
The first reaction step of process (C) according to the invention is carried out in the presence of bases. Preferably used bases are alkali metal hydrides, such as, for example, sodium hydride, alkyllithium, such as n-butyllithium, lithiumdialkylamides, such as, for example, lithium diisopropylamide (LDA), alkali metal alcoholates, such as, for example, sodium methanolate and sodium ethanolate, and metal hydroxides, such as, for example, sodium hydroxide.
For carrying out the first reaction step of process (C) according to the invention, 0.5 to 2 moles, preferably 1 to 1.5 mole, of diester derivative of the formula (IV) and 1 to 3 moles, preferably 1 to 2 moles, of base are generally employed per mole of halogen-substituted pyridinylpyrimidine derivative of the formula (II).
When carrying out the second reaction step of process (C) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0.degree. C. and +150.degree. C., preferably at temperatures between +10.degree. C. and +100.degree. C.
The second reaction step of process (C) according to the invention is carried out in the presence of bases. Preferably used bases are alkali metal hydroxides, such as, for example, sodium hydroxide, and alkali metal carbonates, such as, for example, sodium carbonate.
For carrying out the second reaction step of process (C) according to the invention, 1 to 6 moles, preferably 2.1 to 2.5 moles, of base are generally employed per mole of halogen-substituted pyridinyl-pyrimidine derivative of the formula (II) used.
When carrying out the decarboxylation reaction of process (C) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0.degree. C. and +200.degree. C., preferably at temperatures between +20.degree. C. and +150.degree. C.
The decarboxylation reaction of process (C) according to the invention is carried out in the presence of acids. Preferably used acids are inorganic acids, such as, for example, sulphuric acid or hydrochloric acid, and organic acids, such as, for example, acetic acid.
For carrying out the decarboxylation reaction of process (C) according to the invention, 1 to 10 moles, preferably 2.5 to 6 moles, of acid are generally employed per mole of halogen-substituted pyridinylpyrimidine of the formula (II) used.
Process (C) according to the invention is carried out by customary methods. For working-up, the reaction mixture is neutralized, concentrated and extracted. The product is purified by chromatography or recrystallization.
Process (D-.alpha.) according to the invention for the preparation of the new compounds of the formula (I-d) is preferably carried out using diluents. Suitable diluents for this purpose are virtually all inert organic solvents. These preferably include ethers, such as tetrahydrofuran and dioxane, amides, such as, for example, dimethylformamide, dimethylacetamide and pyridine, and alcohols, such as methanol and ethanol.
When carrying out process (D-.alpha.) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0.degree. C. and +200.degree. C., preferably at temperatures between +50.degree. C. and +150.degree. C.
Process (D-.alpha.) according to the invention is carried out in the presence of bases. Preferably used bases are metal alcoholates, such as, for example, sodium methanolate and sodium ethanolate, and organic bases, such as, for example, trimethylamine, triethylamine and N,N-diethylaniline.
The reaction is carried out and the product is worked up by customary methods by concentration under reduced pressure followed, if appropriate, by chromatographic purification.
For carrying out process (D-.alpha.) according to the invention, 1 to 3 moles, preferably 1 to 1.5 moles, of aryl ketone of the formula (VI) and 0.1 to 5 moles, preferably 0.1 to 2.5 moles, of base are generally employed per mole of picolineamidine derivative of the formula (V).
Process (D-.beta.) according to the invention for the preparation of the new compounds of the formula (I-d) is preferably carried out using diluents. Suitable diluents for this purpose are ethers, such as tetrahydrofuran and dioxane, amides, such as, for example, dimethylformamide, dimethylacetamide and pyridine, water, or mixtures of the solvents mentioned.
When carrying out process (D-.beta.) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0.degree. C. and +200.degree. C., preferably at temperatures between +50.degree. C. and +150.degree. C.
Process (D-.beta.) according to the invention is carried out in the presence of bases. Preferably used bases are inorganic bases, such as sodium hydroxide, potassium hydroxide or potassium carbonate, or organic bases, such as sodium methanolate, triethylamine or N,N-diethylaniline.
For working-up after the reaction, inorganic salts which have formed are filtered off. The filtrate is concentrated and, if appropriate, purified by chromatography or recrystallization.
For carrying out process (D-.beta.) according to the invention, 1 to 3 moles, preferably 1 to 1.5 moles, of acetal of the formula (VII) and 0.01 to 3, preferably 0.1 to 1 mole, of base are generally employed per mole of picolineamidine derivative of the formula (V).
Process (D-.gamma.) according to the invention is carried out in the presence of bases. Preferably used bases are alkali metal alcoholates, such as, for example, sodium methanolate and sodium ethanolate, and organic bases, such as triethylamine and N,N-diethylaniline.
For carrying out process (D-.gamma.) according to the invention, 1 to 3 moles, preferably 1 to 1.5 moles, of 1,3-dioxo derivative of the formula (VIII) and 0.1 to 5 moles, preferably 0.1 to 2.5 moles, of base are generally employed per mole of picolineamidine derivative of the formula (V).
For carrying out process (D-.gamma.) according to the invention, the reaction mixture is stirred for several hours at the required temperature. The reaction product is worked up and isolated by customary methods.
Process (D) according to the invention, variant (.delta.), is preferably carried out in the absence of diluents. However, it is also possible to use one of the following diluents: aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as, for example, acetonitrile and propionitrile, amides, such as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and dimethyl sulphoxide, tetramethylenesulphone and hexamethylphosphoric triamide.
When carrying out process (D) according to the invention, variant (.delta.), the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0.degree. C. and +200.degree. C., preferably at temperatures between +50.degree. C. and +150.degree. C.
For carrying out process (D-.delta.) according to the invention, 1 to 5 moles, preferably 1 to 3 moles, of diacetal of the formula (IX) are generally employed per mole of picolineamidine derivative of the formula (V).
To carry out process (D-.delta.) according to the invention, the reaction mixture is stirred for several hours at the required temperature. Working-up is carried out by customary methods by concentration under reduced pressure followed by chromatographic purification.
The active compounds according to the invention have a powerful action against pests and can be employed in practice for combating undesired harmful organisms. The active substances are suitable for use as fungicides.
Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
Some causative organisms of fungal diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation:
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
In this context, the active compounds according to the invention can be employed with particularly good success for combating diseases in fruit and vegetable growing, such as, for example, against the organism causing tomato rot (Phytophthora) and for protective treatment for example against apple scab (Venturia inaequalis), gray mold on beans (Botrytis cinerea), against Erysiphe graminis on wheat or barley, and against the organism causing leaf spot on barley (Cochliobolus sativus).
Some of the active compounds according to the invention furthermore show a good fungicidal action against Septoria nodorum, Pyrenophora teres, against Fusarium culmorum, Fusarium nivaele and against Pyricularia oryzae and Pellicularia sasakii. Some of the active compounds according to the invention also show a good and broad in-vitro action.
Depending on their particular physical and/or chemical properties, the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine capsules in polymeric substances and in coating compositions for seed, as well as ULV cold-mist and warm-mist formulations.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants, such as halogenohydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumin hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, as well as in mixtures with fertilizers and growth regulators.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing on and the like. It is furthermore possible to apply the active compounds by the ultra-low volume method or to inject the active compound formulation or the active compound itself into the soil. The seeds of the plants can also be treated.
In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.
In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the place of action.